Coated article

ABSTRACT

To provide a plastic spectacle lens which has a very durable hard coat layer and primer layer and prevents the cracking and peeling off of the layer and a reduction in the hardness of the layer, and other coated articles. This coated article has a coat layer containing titanium oxide and an organic Co(II)compound on the surface of a substrate.

FIELD OF THE INVENTION

[0001] The present invention relates to an article coated with a resinfilm, particularly a coated plastic lens having a titaniumoxide-containing resin coat layer, other coated articles and acomposition for forming a titanium oxide-containing resin coat layer.

DESCRIPTION OF THE PRIOR ART

[0002] Since plastic spectacle lenses have such a defect that they areeasily scratched, a silicon-based resin or other hard coat layer hasbeen conventionally formed on the surface of a plastic lens substrate. Aprimer layer made from a resin such as an urethane-based resin has alsobeen formed between this hard coat layer and the surface of thesubstrate to improve the adhesion of the hard coat layer and the impactresistance of a plastic lens.

[0003] However, when a silicone-based hard coat layer is formed on ahigh-refractive resin lens having a refractive index of 1.50 or more, aninterference fringe is formed by the difference of refractive indexbetween the resin lens and the hard coat layer (or primer layer),thereby worsening the appearance of the lens. To solve this problem,JP-A 7-325201 and JP-A 10-332902 (the term “JP-A” as used herein meansan “unexamined published Japanese patent application”) propose theaddition of an oxide having a high refractive index such as titaniumoxide (TiO₂) (or a composite oxide containing TiO₂) to a hard coat orprimer to reduce the difference of refractive index between the hardcoat layer or primer layer and the substrate so as to prevent aninterference fringe.

[0004] JP-A 11-131021 discloses a composition for coating comprising thefollowing essential ingredients:

[0005] (A) a composite oxide fine particle of tin oxide, titanium oxideand zirconium oxide;

[0006] (B) a silane compound having at least one polymerizable reactivegroup; and

[0007] (C) an epoxy (meth)acrylate having a glycidyl group and(meth)acryloyl group in one molecule at the same time.

[0008] In the above publication, a silanol or epoxy compound curingcatalyst may be added and acetylacetonato containing Co(II) as thecenter metal is enumerated as one example of the curing catalyst.

[0009] However, the hard coat layer or primer layer containing titaniumoxide has such problems as the cracking and peeling off of the layer anda reduction in the hardness of the layer due to insufficient durability.

SUMMARY OF THE INVENTION

[0010] It is an object of the present invention to provide a coatedarticle which has a highly durable resin coat layer containing titaniumoxide and prevents the cracking and peeling off of the layer and areduction in the hardness of the layer.

[0011] It is another object of the present invention to provide aplastic lens which has a highly durable hard coat layer or primer layerand prevents the cracking and peeling off of the layer and a reductionin the hardness of the layer.

[0012] It is still another object of the present invention to provide asolution composition for forming a hard coat layer for a plastic lens.

[0013] A further object of the present invention is attained by asolution composition for forming a primer layer for a plastic lens.

[0014] Other objects and advantages of the present invention will becomeapparent from the following description.

[0015] Firstly, according to the present invention, the above objectsand advantages-of the present invention are attained by a coated articlecomprising a substrate and a coat layer made from a resin compositioncontaining titanium oxide and an organic Co(II) compound and formed onthe surface of the substrate.

[0016] Secondly, according to the present invention, the above objectsand advantages of the present invention are attained by a plastic lenswhich comprises a plastic lens substrate having a refractive index of1.50 or more and a hard coat layer formed on the surface of thesubstrate directly or through a primer layer, the hard coat layercomprising:

[0017] (1) 2 to 70 wt % of titanium oxide or a composite oxide thereofhaving a particle diameter of 1.0 to 100 nm;

[0018] (2) 0.1 to 10 wt % of an organic Co(II) compound;

[0019] (3) 20 to 97.9 wt % of a silicon resin; and

[0020] (4) 0.001 to 10 wt % of a curing catalyst, and having arefractive index of 1.48 or more and a thickness of 0.1 to 5 μm, theweight percentages of the above components (1), (2) and (3) being basedon 100 wt % of the total weight of the components (1), (2) and (3), andthe weight percentage of the above component (4) being based on thetotal weight of the above components (1), (2) and (3).

[0021] Thirdly, the above objects and advantages of the presentinvention are attained by a plastic lens which comprises a plastic lenssubstrate having a refractive index of 1.50 or more, a primer layerformed on the surface of the substrate, and a hard coat layer comprisinga silicone resin as a resin component and formed on the surface of theprimer layer, the primer layer comprising:

[0022] (1) 2 to 70 wt % of titanium oxide or a composite oxide thereofhaving a particle diameter of 1.0 to 100 nm;

[0023] (2) 0.1 to 10 wt % of an organic Co(II) compound; and

[0024] (3) 20 to 97.9 wt % of an urethane resin, and having a refractiveindex of 1.48 or more and a thickness of 0.5 to 5 μm, the weightpercentages of the above components (1), (2) and (3) being based on 100wt % of the total weight of the components (1), (2) and (3).

[0025] In the fourth place, according to the present invention, theabove objects and advantages of the present invention are attained by asolution composition for forming a hard coat layer which comprises:

[0026] (1) 2 to 70 wt % in terms of solid content of a sol containingtitanium oxide or a composite oxide thereof having a particle diameterof 1.0 to 100 nm dispersed in water or an organic medium;

[0027] (2) 0.1 to 10 wt % of an organic Co(II) compound;

[0028] (3) 20 to 97.9 wt % of an epoxy group-containing silicon compoundrepresented by the following formula (1):

R¹R² _(a)Si(OR³)_(3-a)  (1)

[0029]  wherein R¹ is a group having an epoxy group and 2 to 12 carbonatoms, R² is an alkyl group or halogenoalkyl group having 1 to 6 carbonatoms, alkenyl group having 2 to 6 carbon atoms, phenyl group orhalogenophenyl group, R³ is a hydrogen atom, alkyl group or acyl grouphaving 1 to 4 carbon atoms, and a is 0, 1 or 2,

[0030] or a partial hydrolysate thereof; and

[0031] (4) 0.001 to 10 wt % of a curing catalyst, the weight percentagesof the above components (1), (2) and (3) being based on 100 wt % of thetotal weight of the components (1), (2) and (3), and the weightpercentage of the above component (4) being based on the total weight ofthe above components (1), (2) and (3).

[0032] In the fifth place, according to the present invention, the aboveobjects and advantages of the present invention a are attained by asolution composition for forming a primer layer comprising:

[0033] (1) 2 to 70 wt % in terms of solid content of a sol containingtitanium oxide or a composite oxide thereof having a particle diameterof 1.0 to 100 nm dispersed in water or an organic medium;

[0034] (2) 0.1 to 10 wt % of an organic Co(II) compound;

[0035] (3) 10 to 87.9 wt % of a polyol; and

[0036] (4) 10 to 87.9 wt % of a polyisocyanate, the weight percentagesof the above components (1), (2), (3) and (4) being based on 100 wt % ofthe total weight of all the components.

[0037] The present invention will be described in detail hereinafter.

[0038] A description is first given of the coated article of the presentinvention.

[0039] The coat layer of the coated article is made from a resincomposition containing titanium oxide and an organic Co(II) compound.

[0040] Co(II) is characterized in that it has an absorption peak at awavelength of 420 to 550 nm and an organic compound having Co(III) withthe main absorption peak at a wavelength of 600 to 800 nm cannot be usedin the present invention because it does not have the effect of theorganic Co(II) compound of the present invention.

[0041] When the titanium oxide-containing resin coat layer contains anorganic Co(II) compound and this coat layer is irradiated withultraviolet rays from sunlight, fluorescent light or other light,ultraviolet rays collide with a titanium oxide particle contained in thecoat layer. The titanium oxide particle is excited by ultraviolet rays,thereby forming electrons excited to a conduction band and electronholes having a valence band. The exited electrons and electron holesmove toward a polymer in the coat layer, reach the polymer and try tocause an optical catalytic reaction there to decompose the polymer bydissociating a bond, for example, a C—C bond in the polymer. When theorganic Co(II) compound is existent in this coat layer, part of excitedenergy of titanium oxide moves toward the organic Co(II) compound and isconverted into heat. Thereby, the decomposition of the polymer issuppressed, thereby retarding the deterioration of the coat layer. As aresult, the adhesion of the coat layer to the substrate is retained, thecracking of the coat layer hardly occurs, and the hardness of the coatlayer is maintained. Since the excitation energy of titanium oxide isabout 3 eV, it-is desired that a compound containing this metal ionshould have an energy gap corresponding to 2.1 to 2.8 eV in order toreceive this energy efficiently. The wavelength of an optical absorptionband corresponding to this energy gap is 420 to 550 nm. Therefore, anorganic Co(II) compound having an optical absorption peak at 420 to 550nm is effective. However, it cannot be said that all compounds havingthis energy gap can receive this energy.

[0042] Preferably, the organic. Co(II) compound having an absorptionpeak at a wavelength of 420 to 550 nm used in the present inventiondissolves in a solvent for a titanium oxide-containing resin coat layer,such as an alcohol or propylene glycol ether, has compatibility with theresin component of the coat layer and does not impede the physicalproperties of the resin of the coat layer. Preferred examples of thecompound include the above Co(II) ion chelate compounds and fatty acidsalts.

[0043] The ligand of the chelate compound is preferably what contains analiphatic chelate structure, as exemplified by acetylacetone,di-n-butoxide-mono-ethyl acetate, di-n-butoxide-mono-methyl acetate,methyl ethyl ketooxime, 2,4-hexanedione, 3,5-heptanedione andacetooxime. A preferred example of the chelate compound is cobalt (II)acetylacetonato.

[0044] Preferred examples of the acid of the fatty acid compound include2-ethyl-hexylic acid, stearic acid, lauric acid, oleic acid, aceticacid, sebacic acid, dodecane diacid, propionic acid, brassylic acid,isobutylic acid, citraconic acid and tetraethylene diamine tetraaceticacid. The fatty acid compound is, for example, a cobalt(II) salt of2-ethyl-hexylic acid.

[0045] Examples of the resin component of the resin coat layer in thepresent invention include silicon resin, urethane resin, acrylic resin,methacrylic resin, allyl resin, polyester resin, polycarbonate resin,epoxy resin and urethane acrylic resin. The resin coat layer containstitanium oxide and an organic Co(II) compound in addition to the aboveresin component. The amount of titanium oxide is preferably 2 to 70 wt %and the amount of the organic Co(II) compound is preferably 0.1 to 10 wt%. The resin coat layer preferably has a refractive index of 1.48 ormore. The amount of titanium oxide is more preferably 10 to 70 wt %, themost preferably 15 to 60 wt %. The amount of the organic Co(II) compoundis more preferably 0.2 to 5 wt %.

[0046] The above titanium oxide may have an amorphous structure butpreferably a rutile, anatase or brookite crystal structure. Preferably,at least ½, that is, at least 50% of the amount of titanium oxide has atleast one of rutile, anatase or brookite crystal structures. Out ofthese crystal structures, the rutile type is more preferred and at least½, that is, 50% of the amount of titanium oxide has a rutile typecrystal structure. However, as rutile type titanium dioxide is moreexpensive than anatase type titanium dioxide, anatase type titaniumdioxide is preferably used from an economical point of view. Thetitanium oxide may be a titanium oxide fine particle or a compositeoxide of titanium and at least one element selected from the groupconsisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr and In. Examplesof the composite oxide include a composite oxide fine particle oftitanium and iron (TiO₂•Fe₂O₃), composite oxide fine particle oftitanium and silicon (TiO₂•SiO₂), composite oxide fine particle oftitanium and cerium (TiO₂•CeO₂), composite oxide fine particle oftitanium, iron and silicon (TiO₂•Fe₂O₃•SiO₂), composite oxide fineparticle of titanium, iron and cerium (TiO₂•CeO₂•SiO₂), composite oxidefine-particle of titanium, zirconium and silicon (TiO₂•ZrO₂•SiO₂) andcomposite oxide fine particle of titanium, aluminum and silicon(TiO₂•Al₂O₃•SiO₂).

[0047] The titanium oxide fine particle or titanium composite oxide fineparticle can be obtained by any known method. For example, a hydroustitanic acid gel or sol is prepared by adding an alkali to an aqueoussolution of a titanium salt such as titanium chloride or titaniumsulfate for neutralization or bypassing an aqueous solution of atitanium salt through an ion exchange resin. Thereafter, hydrogenperoxide water is added to the hydrous titanic acid gel or sol, or amixture thereof to dissolve the hydrous titanic acid so as to prepare auniform aqueous solution. Further, titanic acid is hydrolyzed by heatingto obtain a titanium oxide sol containing titanium oxide dispersedtherein. In the step before the heat treatment, an inorganic compound ofone element or two or more elements selected from the group consistingof Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr and In is added to obtain acomposite oxide sol. For example, JP-A 63-185820 discloses a process forproducing a silica-titanium or titanium-silica-zirconia composite oxidesol.

[0048] Further, the surface of the above titanium oxide fine particle ortitanium composite oxide fine particle may be surface coated with (onelayer or two or more layers of) silicon oxide, a mixture of siliconoxide and an oxide of at least one element selected from the groupconsisting of Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr and In, or acomposite oxide. The fine particle can be obtained by any known method.For example, JP-A 8-48940 discloses a process for producing a compositeoxide sol by coating a titanium-silica composite oxide fine particlewith silica-zirconia composite oxide. When titanium oxide is existent inthe form of a composite oxide fine particle or surface coated fineparticle, the weight of a metal oxide other than titanium oxidecontained in the fine particle is excluded (ignored) in the calculationof the amount of titanium oxide.

[0049] The titanium oxide may be amorphous but preferably has an anataseor rutile crystal structure. Particularly preferably, the titanium oxidehas a rutile crystal structure.

[0050] When the titanium oxide is a composite oxide fine particle, toimprove its dispersibility in a solvent, the surface of the compositeoxide fine particle can be modified by an organic silane compound or anamine. The amount of the organic silane compound is 0 to 20 wt % basedon the weight of the fine particle. This surface modification may becarried out while an organic silane compound having a hydrolyzable groupis not hydrolyzed or after it is hydrolyzed.

[0051] The organic silane compound for modifying the surface of thecomposite oxide fine particle is, for example, an organic silanerepresented by the formula R₃SiX, R₂SiX₂, RSiX₃ or SiX₄ (R is an organicgroup having alkyl, phenyl, vinyl, methacryloxy, mercapto, amino, epoxyor ureide and X is a hydrolyzable group), such as trimethylmethoxysilane, diphenyl dimethoxysilane, vinyl trimethoxysilane,γ-methacryloxypropyldimethyl methoxysilane, γ-aminopropyltriethoxysilane, glycidoxypropyl trimethoxysilane, γ-ureidepropyltriethoxysilane or tetraethyl orthosilicate.

[0052] Examples of the amine for modifying the surface of the fineparticle include alkylamines such as ammonium and ethylamine,aralkylamines such as benzylamine, alicyclic amines such as piperidineand alkanolamines such as monoethanolamine.

[0053] To modify the surface of the fine particle with an organicsilicon compound or amine, for example, a composite oxide fine particleis mixed with an alcohol solution of the compound, a predeterminedamount of water and optionally a catalyst are added, and the resultingmixture is left to stand at normal temperature for a predetermined timeor heated. The surface of the composite oxide fine particle can bemodified by adding a hydrolysate of the compound and a composite oxidefine particle to a mixture of water and an alcohol and by heating.

[0054] The resin coat layer of the present invention may contain aninorganic oxide, antioxidant, ultraviolet light absorber, levelingagent, lubricity modifier, antistatic agent, bluing agent and the likeas required in addition to the above resin, titanium oxide and organicCo(II) compound. The inorganic oxide is an oxide or composite oxide ofat least one element selected from the group consisting of Si, Al, Sn,Sb, Ta, La, Zn, W, Zr and In and a fine particle having a particlediameter of 1 to 100 nm. The inorganic oxide may be contained in anamount of 0 to 70 wt % in terms of nonvolatile content.

[0055] The above antioxidant is preferably what has a sulfide structure(C—S—C structure), more preferably a hindered phenolic compound having asulfide structure. Examples of the antioxidant include4,4′-thiobis(3-methyl-6-t-butylphenol),2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine,didodecyl 3,3′-thiobispropionate, dioctadecyl3,3′-thiobispropionate,dimyristyl 3,3′-thiobispropionate and2,4-[bis(octylthio)methyl]-O-cresol. The antioxidant is preferablycontained in an amount of 5 wt % or less.

[0056] The leveling agent or lubricity modifier is preferably acopolymer of polyoxyalkylene and polydimethylsiloxane or a copolymer ofpolyoxyalkylene and fluorocarbon. They are preferably used in an amountof 0.001 to 10 parts by weight based on the total amount of the coatingsolution.

[0057] The thickness of the resin coat layer in the present invention,which differs according to the purpose of a resin coated article, ispreferably 0.10 to 10 μm.

[0058] The coated article of the present invention is produced bycoating the surface of the substrate with a coating solution for a resincoat layer by dip coating, spinner coating, spray coating or flowcoating and drying the coating solution to form a film and heating thefilm thus formed on the surface of the substrate at a temperature lowerthan the heat resistant temperature of the substrate.

[0059] When an ultraviolet curable resin is used as a matrix componentof the coating solution for a resin coat layer, the coated article ofthe present invention can be produced by coating the surface of thesubstrate with the coating solution and irradiating the surface of thesubstrate coated with the coating solution with ultraviolet radiationhaving a predetermined wavelength to cure the resin.

[0060] The coated article of the present invention can be a plastic lenshaving a hard coat layer directly on the surface of a substrate. In thiscase, the titanium oxide-containing a resin coat layer in the presentinvention is used as the hard coat layer. The coated article of thepresent invention can be a plastic lens having a primer layer and a hardcoat layer formed on the surface of a substrate in the order named. Inthis case, the titanium oxide-containing resin coat layer of the presentinvention is used as either one or both of the primer layer and hardcoat layer.

[0061] A preferred mode of the titanium oxide-containing resin coatlayer of the present invention is a hard coat layer of a titaniumoxide-containing silicon resin having a refractive index of 1.48 or moreand a thickness of 0.1 to 5 μm formed on the surface of the substrate ofa plastic lens having a refractive index of 1.50 or more directly orthrough a primer layer.

[0062] Another preferred mode of the titanium oxide-containing resincoat layer of the present invention is a primer layer of a titaniumoxide-containing urethane resin having a refractive index of 1.48 ormore and a thickness of 0.5 to 5 μm formed between the surface of thesubstrate of a plastic lens having a refractive index of 1.5.0 or moreand a hard coat layer of a silicon resin having a refractive index of1.48 or more formed thereon.

[0063] Still another preferred mode of the titanium oxide-containingresin coat layer of the present invention is a combination of a primerlayer and a hard coat layer in a plastic lens which comprises thesurface of the substrate of a plastic lens having a refractive index of1.50 or more, a primer layer of a titanium oxide-containing urethaneresin having a thickness of 0.5 to 5 μm formed on the surface of thesubstrate and a hard coat layer of a titanium oxide-containing siliconresin having a refractive index of 1.48 or more and a thickness of 0.1to 5 μm formed on the primer layer. That is, the titaniumoxide-containing resin coat layer of the present invention is used asthe both layers.

[0064] The hard coat layer when the titanium oxide-containing siliconresin coat layer of the present invention is formed on the surface of aplastic lens substrate as a hard coat layer will be described in detailhereinafter.

[0065] Hard Coat Layer

[0066] A coating solution (solution composition) for forming a siliconehard coat layer will be described.

[0067] The coating solution for forming a hard coat layer comprises thefollowing components (1) to (4):

[0068] (1) 2 to 70 wt % in terms of solid content of a sol containingtitanium oxide or a composite oxide thereof having a particle diameterof 1.0 to 100 nm dispersed in water or an organic medium;

[0069] (2) 0.1 to 10 wt % of an organic Co(II) compound;

[0070] (3) 20 to 97.9 wt % of an epoxy group-containing silicon compoundrepresented by the following formula (1):

R¹R² _(a)Si(OR³)_(3-a)  (1)

[0071]  wherein R¹ is a group having an epoxy group and 2 to 12 carbonatoms, R² is an alkyl group or halogenoalkyl group having 1 to 6 carbonatoms, alkenyl group having 2 to 6 carbon atoms, or phenyl group orhalogenophenyl group, R³ is a hydrogen atom, alkyl group or acyl grouphaving 1 to 4 carbon atoms, and a is 0, 1 or 2,

[0072] or a partial hydrolysate thereof; and

[0073] (4) 0.001 to 10 wt% of a curing catalyst.

[0074] The components (1) and (2) have already been described above.

[0075] Examples of the epoxy group-containing silicon compound as thecomponent (3) include γ-glycidoxypropyl trimethoxysilane,β-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane,β-glycidoxypropyl triethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyl diethoxysilane andβ-(3,4-epoxycyclohexyl)ethyl trimethoxysilane.

[0076] Examples of the curing catalyst (4) of the composition forforming a hard coat layer include alkali metal salts and ammonium saltsof carboxylic acids, metal salts and ammonium salts of acetylacetone,metal salts of ethyl acetoacetate, metal salts coordinated withacetylacetone and ethyl acetoacetate, metal salt hydrates of ethylenediamine, primary to tertiary amines, polyalkylene amines, sulfonates,magnesium perchlorate, ammonium perchlorates, and combinations of thesecompounds and organic mercaptan or mercaptoalkylenesilane. The curingcatalyst may be added when a composition for forming a hard coat layeris prepared or right before a composition for forming a hard coat layeris applied.

[0077] The weight percentages of the above components (1), (2) and (3)are based on 100 wt % of the total weight of the components (1), (2) and(3), and the weight percentage of the above component (4) is based onthe total weight of the above components (1), (2) and (3).

[0078] The amount of the component (1) is preferably 5 to 60 wt %,. theamount of the component (2) is preferably 0.2 to 5 wt %, and the amountof the component (3) is preferably 35 to 94.8 wt %. The amount of thecomponent (4) is preferably 0.01 to 8 wt %.

[0079] The coating solution for forming a hard coat layer may containthe following components (D) and (E) as required in addition to theabove components (1) to (4).

[0080] Component (D)

[0081] A fine particle of an oxide of at least one element selected fromthe group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr andIn, such as SiO₂, Al₂O₃, SnO₂, Sb₂O₅, Ta₂O₅, CeO, La₂O₃, Fe₂O₃, ZnO,WO₃, Zro₂ or In₂O₃ in the form of a sol solution and having a particlediameter of 1.0 to 100 nm may be contained in a total amount of 80 wt %or less.

[0082] When the fine particle is a composite oxide, its surface may bemodified by an organic silane compound or amine to improve itsdispersibility in a solvent. It should be understood that surfacemodification is completely the same as that for a titanium compositeoxide. When the above titanium oxide is a titanium composite oxide, forexample, a TiO₂—ZrO₂—SiO₂ composite oxide fine particle, a metal oxideother than titanium oxide contained in the composite oxide, for example,zirconium oxide and silicon oxide are the components (D).

[0083] The fine particle of the component (D) is preferably dispersed inwater or an organic solvent such as an alcohol in an amount of 5 to 80wt %. The fine particle of the component (D) is contained in the coatingsolution for forming a hard coat layer in an amount of 70 wt % or lessin terms of solid content.

[0084] Component (E)

[0085] The component (E) is an antioxidant, preferably an antioxidanthaving a C—S—C structure as described above.

[0086] The following components (F-1) to (F-14) which can react with ahydrolyzed silanol group and epoxy group may be used to improve physicalproperties such as dyability, heat resistance, water resistance,antistatic properties and surface hardness or assist a catalyticfunction, in addition to the above components (A) to (E).

[0087] Component (F-1)

[0088] The component (F-1) is an organic compound having only one OH orSH group in the molecule, at least one group selected from the groupconsisting of —O—, —CO—O—, —S—, —CO—S— and —CS—S— in the molecular mainchain and further at least one unsaturated group and soluble in water ora lower alcohol having 4 or less carbon atoms.

[0089] The above compound is preferably a compound represented by thefollowing formula (2):

R⁴—X—R⁵YH  (2)

[0090] wherein R⁴ is a monovalent hydrocarbon group having at least oneunsaturated group and may contain oxygen and sulfur atoms, R⁵ is adivalent hydrocarbon group having 2 or more carbon atoms and may containoxygen and sulfur atoms, and X and Y are each independently an oxygenatom or sulfur atom.

[0091] Examples of the compound represented by the above formula (2)include polyethylene glycol monomethacrylate,poly(butanediol)monoacrylate, poly(butanediol)monomethacrylate,1,4-butanediol monovinyl ether, 1,6-hexanedithiol monoacrylate,di(acryloxyethyl)hydroxyethylamine, 2-hydroxy-3-phenoxypropyl acrylate,pentaerythritol triacrylate, 2-hydroxybutyl acrylate,3-acryloyloxyglycerin monomethacrylate,2-hydroxy-1,3-dimethacryloxypropane and 2-mercaptoethyl acrylate.

[0092] Out of the above compounds of the formula (2), preferred arecompounds represented by the following formula (3):

[0093] wherein R⁶ is a hydrogen atom or methyl group, and b is aninteger of 2 to 10, preferably 4 to 6, compounds represented by thefollowing formula (4):

[0094] wherein R⁶ is a hydrogen atom or methyl group, R⁷is —CH₂CH₂—,—CH₂CH(CH₃)— or —CH(CH₃)CH₂—, and c is an integer of 2 to 9, preferably2 to 4,

[0095] compounds represented by the following formula (5):

CH₂═CH—(CH₂)_(d)—O—(CH₂)_(b)—OH  (5)

[0096]  wherein b is an integer of 4 to 10, and d is 0 or 1, andcompounds represented by the following formula (6):

CH₂═CH—(CH₂)_(d)—O—(OR⁷)_(c)—OH  (6)

[0097]  wherein R⁷ is —CH₂CH₂—, —CH₂CH(CH₃)— or —CH(CH₃)CH₂—, c is aninteger of 2 to 9, and d is 0 or 1.

[0098] The compounds of the above formula (3) include 4-hydroxybutylacrylate and 4-hydroxybutyl methacrylate.

[0099] The compounds of the above formula (4) include diethylene glycolmonoacrylate, tetraethylene glycol monoacrylate, polyethylene glycolmonoacrylate, tripropylene glycol monoacrylate, polypropylene glycolmonoacrylate, diethylene glycol monomethacrylate, tetraethylene glycolmonomethacrylate, polyethylene glycol monomethacrylate, tripropyleneglycol monomethacrylate and polypropylene glycol monomethacrylate.

[0100] The compounds of the above formula (5) include4-hydroxybutylallyl ether and 4-hydroxybutylvinyl ether.

[0101] The compounds of the above formula (6) include diethylene glycolmonoallyl ether and triethylene glycol monovinyl ether.

[0102] The above component (F-1) is used in an amount of 0.001 to 50 wt% based on the total solid content of the base resin.

[0103] Component (F-2)

[0104] The component (F-2) is an-unsaturated dibasic acid. Examples ofthe component (F-2) include itaconic acid, succinic acid, malonic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,sebacic acid, fumaric acid and maleic acid.

[0105] Component (F-3)

[0106] The component (F-3) is an cyclic anhydride of an unsaturateddibasic acid. Examples of the component (F-3) include succinicanhydride, glutaric anhydride, trimellitic anhydride, pyromelliticanhydride, phthalic anhydride and maleic anhydride.

[0107] Component (F-4)

[0108] The component (F-4) is an imide compound of an unsaturateddibasic acid. Examples of the component (F-4) include succinic acidimide, glutaric acid imide, phthalic acid imide and maleic acid imide.

[0109] Component (F-5)

[0110] The component (F-5) is a saturated polycarboxylic acid. Examplesof the component (F-5) include adipic acid and suberic acid.

[0111] Component (F-6)

[0112] The component (F-6) is an cyclic anhydride of a saturatedpolycarboxylic acid. Examples of the component (F-6) include cyclicanhydrides of saturated polycarboxylic acids as the component (F-5),such as adipic anhydride.

[0113] Component (F-7)

[0114] The component (F-7) is an imide compound of a saturatedpolycarboxylic acid. Examples of the component (F-7) include cyclicanhydrides of the above saturated polycarboxylic acids (component(F-5)), such as adipic acid imide.

[0115] Component (F-8)

[0116] The component (F-8) is an amine. Examples of the component (F-8)include polymethylene diamine, polyether diamine, diethylene triamine,iminobispropylamine, bishexamethylene triamine, diethylene triamine,tetraethylene pentaamine, pentaethylene hexaamine, pentaethylenehexamine, dimethylamino propylamine, aminoethyl ethanolamine,methyliminobispropylamine, menthanediamine, N-aminomethyl piperazine,1,3-diaminocyclohexane, isophorone diamine, metaxylene diamine,tetrachloroparaxylene diamine, methaphenilene diamine, 4,4-methylenedianiline, diaminodiphenylsulfone, benzidine, toluidine, diaminodiphenylether, 4,4′-thiodianiline, 4,4′-bis(o-toluidine)dianisidine, o-phenylenediamine, 2,4-toluene diamine, methylenebis(o-chloroaniline),diaminiditolylsulfone, bis(3,4-diaminophenyl)sulfone,2,6-diaminopyridine, 4-chloro-o-phenylene diamine,4-methoxy-6-methyl-m-phenylene diamine, m-aminobenzylamine,N,N,N′,N′-tetramethyl-1,3-butane diamine,N,N,N′,N′-tetramethyl-p-phenylene diamine, tetramethyl guanidine,triethanol amine, 2-dimethylamino-2-hydroxypropane,N,N′-dimethylpiperazine, N,N′-bis[(2-hydroxy)propyl]piperazine,N-methylmorpholine, hexamethylene tetramine, pyridine, piperazine,quinoline, benzyldimethylamine, α-methylbenzylmethylamine,2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethylol)phenol,N-methylpiperazine, pyrrolidine and morpholine.

[0117] An adduct of the above mine with an organic carboxylic acid,cyclic ether, ketone, aldehyde or hydroquinone, or a condensate of theabove amine may be used like the above amines.

[0118] Component (F-9)

[0119] The component (F-9) is urea and a formaldehyde adduct thereof.

[0120] Component (F-10)

[0121] The component (F-10) is an alkyl-substituted methylol melamine.

[0122] Component (F-11)

[0123] The component (F-11) is a compound having two or more OH groupsor SH groups. Examples of the component (F-11) include 1,4-butanediol,1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, ethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol,polyethylene glycol, propylene glycol, tripropylene glycol,polypropylene glycol, trimethylol propane, neopentyl glycol, catechol,resorcinol, alkylene glycol, polyvinyl alcohol, polycaprolactone diol,polycaprolactone triol and polycaprolactone tetraol.

[0124] Component (F-12)

[0125] The component (F-12) is a compound having two or more epoxygroups. Examples of the component (F-12) include glycidyl ethers ofpolyhydric alcohols as the component (F-11).

[0126] Component (F-13)

[0127] The component (F-13) is a dicyandiamide, hydrazide, thiourea,guanidine, ethyleneimine, sulfoneamide or derivative thereof.

[0128] Component (F-14)

[0129] The component (F-14) is an organic silicon compound representedby the following formula (7):

R⁸ _(f)R⁹ _(e)Si(OR¹⁰)_(4-f-e)  (7)

[0130] wherein R⁹ is an alkyl group having 1 to 6 carbon atoms, arylgroup, alkenyl group, halogenated alkyl group or halogenated aryl group,R¹⁰ is a hydrogen atom, alkyl group having 1 to 4 carbon atoms, acylgroup or alkylacyl group, R⁸ is selected from an alkyl group having 1 to4 carbon atoms, halogenated alkyl group, aryl group and halogenated arylgroup having 6 to 12 carbon atoms, methacryloxyalkyl group having 5 to 8carbon atoms, ureidealkylene group having 2 to 10 carbon atoms, aromaticureidealkylene group, halogenated aromatic alkylene group andmercaptoalkylene group, f is 1, 2 or 3, and e is 0, 1 or 2,

[0131] or a partial hydrolysate thereof.

[0132] The component (F-14) may be added in an amount of 100 parts orless by weight in terms of solid content based on 100 parts by weight ofthe total solid content of the base resin.

[0133] Examples of the compound of the above formula (7) includetrimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane,triethylethoxysilane, triphenylmethoxysilane,diphenylmethylmethoxysilane, phenyldimethylmethoxysilane,phenyldimethylmethoxysilane, vinyldimethylmethoxysilane,vinyldimethylethoxysilane, γ-acryloxypropyldimethylmethoxysilane,γ-methacryloxypropyldimethylmethoxysilane,γ-mercaptopropyldimethylmethoxysilane,γ-mercaptopropyldimethylethoxysilane, N-β(aminoethyl)γ-aminopropyldimethylmethoxysilane, γ-aminopropyldimethylmethoxysilane,γ-aminopropyldimethylethoxysilane,γ-glycidoxypropyldimethylmethoxysilane,γ-glycidoxypropyldimethoxyethoxysilane,β-(3,4-epoxycyclohexyl)ethyldimethylmethoxysilane,dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane,diethyldiethoxysilane, diphenyldimethoxysilane,phenylmethyldimethoxysilane, phenylmethyldiethoxysilane,vinylmethyldimethoxysilane, vinylmethyldiethoxysilane,γ-acryloxypropylmethyldimethoxysilane,γ-methacryloxypropyldimethyldimethoxysilane,γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldime-thoxysilane,γ-aminopropylmethyldiethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethoxydiethoxysilane,β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane,methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane,ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,vinyltrimethoxysilane, vinyltriethoxysilane,vinyl(β-methoxyethoxy)silane, γ-acryloxypropyltrimethoxysilane,γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,β-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,β-glycidoxypropyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, tetraethyl orthosilicateand tetramethyl orthosilicate.

[0134] The above components (F-1) to (F-14) may be added in a totalamount of 0.001 to 70 wt % based on the total solid content of the baseresin.

[0135] The solvent for the composition for forming a hard coat layer isa glycol, aliphatic cyclic ketone, acetate or alcohol. Examples of theglycol include ethylene glycol monomethyl ether acetate, ethylene glycolmonoethyl ether acetate, ethylene glycol monopropyl ether acetate,ethylene glycol monobutyl ether acetate, propylene glycol monomethylether acetate, propylene glycol monoethyl ether acetate, propyleneglycol monopropyl ether acetate, propylene glycol monobutyl etheracetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,ethylene glycol dipropyl ether, ethylene glycol dibutyl ether,diethylene glycol dimethyl ether, diethylene glycol diethyl ether,diethylene glycol dipropyl ether, diethylene glycol dibutyl ether,propylene glycol dimethyl ether, propylene glycol diethyl ether,propylene glycol monomethyl ether, ethylene glycol monoethyl ether andethylene glycol monobutyl ether. Examples of the aliphatic cyclic ketoneinclude cyclohexanone, o-methylcyclohexanone, m-methylcyclohexanone andp-methylcyclohexanone. Examples of the acetate include ethyl acetate,n-propyl acetate and n-butyl acetate. Examples of the alcohol includemethanol, ethanol, 1-propanol and 2-propanol. Solvent naphtha and methylethyl ketone may also be used as a solvent.

[0136] The solvent is used to ensure that the solids content of thecomposition for forming a hard coat layer should be 5 to 50 wt %.

[0137] Water is necessary to hydrolyze the component (C) and thecomponent (F-14) and used in an amount 1.0 to 10 times the theoreticalamount of hydrolysis.

[0138] The composition for forming a hard coat layer may further containa leveling agent, weather ability modifier, antistatic agent, colorantand dye for a cured film. Examples of the leveling agent out of theseinclude a copolymer of polyoxyalkylene and polydimethylsiloxane and acopolymer of polyoxyalkylene and fluorocarbon. The leveling agent isused in an amount of 0.001 to 10 parts by weight in terms of solidcontent in the composition for forming a hard coat layer.

[0139] The composition for forming a hard coat layer is applied to thesurface of the substrate directly or the surface of the primer layerformed on the surface of the substrate and cured. Coating isappropriately selected from dip coating, flow coating, spinner coatingand spray coating. Curing conditions include a temperature of 90 to 120°C. and a time of 30 minutes to 24 hours, for example. The optimumconditions are preferably selected from these conditions.

[0140] The thickness of the hard coat layer is preferably 0.1 to 5 μm.When the thickness of the film is smaller than 0.1 μm, hardness maylower and when the thickness is larger than 5 μm, the film may crack.The thickness of the hard coat layer is more preferably 0.5 to 5 μm.

[0141] A detailed description is subsequently given of a case where thetitanium oxide-containing urethane resin coat layer of the presentinvention is formed on the surface of the plastic lens substrate as aprimer layer.

[0142] Primer Layer

[0143] A solution composition for forming a primer layer (film) containsthe following components (1) to (4):

[0144] (1) 2 to 70 wt % in terms of solid content of a sol containingtitanium oxide or a composite oxide thereof having a particle diameterof 1.0 to 100 nm dispersed in water or an organic medium;

[0145] (2) 0.1 to 10 wt % of an organic Co(II) compound;

[0146] (3) 10 to 87.9 wt % of a polyol; and

[0147] (4) 10 to 87.9 wt % of a polyisocyanate.

[0148] The components (1) and (2) has already described above.

[0149] Examples of the polyol as the component (3) include polyesterpolyols, polyether polyols, acrylic polyols and polycarbonate polyols.Out of these, polyester polyols are preferred.

[0150] The polyester polyols are obtained by carrying out thedehydration condensation of a polybasic acid and a compound havingactive hydrogen. Examples of the polybasic acid include organic acidssuch as isophthalic acid, phthalic acid, phthalic anhydride,hydrogenated phthalic acid, fumaric acid, dimerized linolenic acid,maleic acid and saturated aliphatic dibasic acids having 4 to 8 carbonatoms. These polybasic acids may be used alone or in combination of twoor more. Examples of the compound having active hydrogen include glycolssuch as ethylene glycol, propylene glycol, butylene glycol, hexyleneglycol and diethylene glycol; adducts of trimethylolpropane,hexanetriol, glycerin, trimethylolethane, pentaerythritol,polycaprolactone diol, polycaprolactone triol, polycaprolactone tetraoland bisphenol A with ethylene glycol and propylene; adducts of the abovecompounds with bromine; and diols having a chemical structure composedof 4,4′-thiobisbenzenethiol. These compounds having active hydrogen maybe used alone or in combination of two or more.

[0151] The above polyester polyols may be acquired as commerciallyavailable products such as Demosphen Series (of Sumitomo-Bayer Co.,Ltd.), Nipporan Series (of Nippon Polyurethane Co. Ltd.), Takerac Series(of Takeda Chemical Industries, Ltd.) Adeca New Ace Series (of AsakiDenka Kogyo K. K.) and Barnoc (of Dainippon Ink and Chemicals, Inc.).

[0152] The polycarbonate polyols may be acquired as commerciallyavailable products such as Nipporan 980 Series (of Nippon PolyurethaneCo., Ltd.) and Carbodiol (of Toa Corporation.), the polyether polyolsmay be acquired as commercially available products such asAdecapolyether (of Asahi Denka Kogyo K. K.), Actocall (of TakedaChemical Industries, Ltd.) and PPG-Diol Series (of Mitsui ToatsuChemicals Inc.), and the acrylic polyols may be acquired as commerciallyavailable products such as Takerac (of Takeda Chemical Industries, Ltd.)and Acrydic (of Dainippon Ink and Chemicals, Inc.). They are preferablyused to adjust the physical properties of urethane resins.

[0153] The polyisocyanate may be an aliphatic polyisocyanate orpolyisocyanate having an aromatic ring. The polyisocyanate is preferablydiisocyanate having two or more isocyanate groups (NCO group) in themolecule.

[0154] Examples of the polyisocyanate include hexamethylenediisocyanate, 1,3,3-trimethylhexamethylene diisocyanate, isophoronediisocyanate, 4,4′-dicyclohexylmethane diisocyanate, xylylenediisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylenediisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate,hydrogenated diphenylmethane diisocyanate, 1,5-naphthalene diisocyanateand tetramethylxylylene diisocyanate. These polyisocyanates may be usedas a modified product, isocyanurate, allophanate, burette, carbodiimideor adduct such as trimer.

[0155] The polyisocyanate may be blocked by a blocking agent. Examplesof the blocking agent include acetylacetone, diethyl malonate, dimethylmalonate, 2,4-hexanedione, 3,5-heptanedione, acetooxime, butanoneoxime,methyl ethyl ketooxime and caprolactam. Out of these, β-diketone such asacetylacetone and methyl ethyl ketooxime are preferred.

[0156] The isocyanate blocked by a blocking agent can be synthesized byknown technologies such as methods described in British Patent No.1442024, Polym. Sci. Technol., 36. 197 (1987), and Coating Technology31, 161 (1992).

[0157] When the polyisocyanate is an aromatic polyisocyanate such asxylylene diisocyanate or tetramethylxylene diisocyanate, it can beadvantageously used as a modified product, adduct or prepolymer.

[0158] When the polyisocyanate is an aliphatic polyisocyanate, it isblocked by β-diketone and advantageously used. Particularly whenhexamethylene diisocyanate is used as a cyclic trimer blocked byβ-diketone, the primer composition can be advantageously provided as aone-part type composition.

[0159] The primer composition may contain the above polyol andpolyisocyanate while they are not reacted with each other or may containa prepolymer or thermoplastic (linear) polymer obtained by reacting theabove polyol and polyisocyanate.

[0160] When the primer composition contains the above polyol andpolyisocyanate while they are not reacted with each other, the ratio(NCO/OH) of the number of equivalents of the isocyanate group (NCO) ofthe polyisocyanate to the number of equivalents of the hydroxyl group(OH) of the polyol is preferably in the range of 0.7 to 1.5. When theratio is smaller than 0.7, the adhesion of the hard coat layer to theobtained primer layer may decrease and when the ratio is larger than1.5, the primer layer may whiten or the adhesion of the hard coat layermay lower. The (NCO/OH) ratio is more preferably in the range of 0.8 to1.2.

[0161] In the primer composition, the weight percentages of the abovecomponents (1), (2), (3) and (4) are based on 100 wt % of the totalweight of all the components.

[0162] The amount of the component (1) is preferably 3 to 65 wt %, theamount of the component (2) is preferably 0.2 to 5 wt %, the amount ofthe component (3) is preferably 12 to 84.8 wt %, and the amount of thecomponent (4) is preferably 12.to 84.8 wt %.

[0163] The primer composition may further contain the same oxide fineparticle (component (D)) as in the above hard coat composition in anamount of 80 wt % or less as required to, approximate the refractiveindex of the primer layer to that of the lens.

[0164] The primer composition may optionally contain a curing catalyst,leveling agent, lubricity modifier, weatherability modifier, antistaticagent, colorant, bluing agent and the like. The type and content of thecuring catalyst are the same as the curing catalyst for the abovecomposition for forming a hard coat layer.

[0165] The primer composition in the present invention is provided as anorganic solvent or aqueous solution. Examples of the organic solvent arethe same as those enumerated for the above hard coat, such as glycols,aliphatic cyclic ketones, acetates and alcohols. The solvent is used inan amount of 2 to 50 wt % in terms of solid content in the primercomposition.

[0166] The primer composition is applied to the surface of the substrateand cured. Coating is appropriately selected from dip coating, flowcoating, spinner coating and spray coating. Preferred curing conditionsinclude a temperature of 85 to 120° C. and a time of 15 minutes to 10hours. The optimum conditions are preferably selected from the aboveconditions.

[0167] The thickness of the primer layer is preferably 0.5 to 5 μm. Whenthe thickness is smaller than 0.5 μm, the effect of improving the impactresistance of a coated article is small and when the thickness is largerthan 5 μm, the hardness of the hard coat layer to be formed on theprimer layer may lower.

[0168] An anti-reflection layer which comprises a single-layer ormultiple layers of an inorganic material may be formed on the hard coatlayer. This makes it possible to suppress the reflection of visiblelight and improve visible light transmission and weatherability.Examples of the inorganic material include SiO, SiO₂, Si₃N₄, TiO₂, ZrO₂,Al₂O₃, MgF₂ and Ta₂O₅. The anti-reflection film can be made thin by avacuum deposition method or the like.

[0169] The substrate in the present invention may be a transparentsubstrate made from a plastic such as a polyurethane resin, methacrylicpolymer, allyl polymer or copolymer thereof, or glass having arefractive index of 1.50 or more. Examples of the substrate includesubstrates for use in optical lenses such as spectacle lenses and cameralenses, display element filters, glass sheets for construction, autowindow glass and light covers for use in automobiles.

[0170] To produce the resin coated article of the present invention, asubstrate whose surface has been treated with an alkali, acid orsurfactant, which is polished with inorganic or organic fine particles,or which is subjected to a primer treatment, plasma treatment, coronatreatment or flame treatment may be used as the substrate to improve theadhesion of the coat layer to the lens substrate.

[0171] One preferred mode of the liquid composition for forming a primerlayer for the coated article of the present invention is a liquidcomposition for forming a primer layer which contains the followingcomponents (1) to (4):

[0172] (1) a sol containing titanium oxide or a composite oxide thereofhaving a particle diameter of 1.0 to 100 nm dispersed in water or anorganic solvent;

[0173] (2) a Co(II) chelate compound or fatty acid compound,

[0174] (3) a polyester polyol; and

[0175] (4) a polyisocyanate.

[0176] Preferably, the above component (1) is contained in an amount of2 to 70 wt %, the component (2) in an amount of 0.1 to 10 wt %, thecomponent (3) in an amount of 10 to 87.9 wt % and the component (4) inan amount of 10 to 87.9 wt % in terms of solid content.

[0177] One preferred mode of the coated article of the present inventionis a plastic lens comprising a substrate having a refractive index of1.50 or more and a hard coat layer which is essentially composed of asilicon resin, has a thickness of 0.1 to 5 μm and a refractive index of1.48 or more, and is formed on the surface of the plastic lens substratedirectly or through a primer layer, the hard coat layer comprising:

[0178] (1) 2 to 70 wt % of titanium oxide or a composite oxide thereofhaving a particle diameter of 1.0 to 100 nm;

[0179] (2) 0.1 to 10 wt % of a Co(II) chelate compound or fatty acidcompound;

[0180] (3) 20 to 97.9 wt % of a silicon-based resin; and

[0181] (4) 0.001 to 10 wt % of a curing catalyst.

[0182] Another preferred mode of the coated article of the presentinvention is a plastic lens comprising a substrate having a refractiveindex of 1.50 or more, a primer layer which is essentially composed ofan urethane resin and has a thickness of 0.5 to 5 μm and a refractiveindex of 1.48 or more, and a hard coat layer which is essentiallycomposed of a silicon resin, are formed on the surface of the substratein the order named, the primer layer comprising:

[0183] (1) 2 to 70 wt % of titanium oxide or a composite oxide thereofhaving a particle diameter of 1.0 to 100 nm;

[0184] (2) 0.1 to 10 wt % of a Co(II) chelate compound or fatty acidcompound; and

[0185] (3) 20 to 97.9 wt % of an urethane-based resin.

EXAMPLES

[0186] The following examples are provided for the purpose of furtherillustrating the present invention but are in no way to be taken aslimiting.

[0187] Preparation of Primer Coat Solutions 1 to 5

[0188] 64 g of a polyester polyol comprising isophthalic acid and1,6-hexanediol and having an average molecular weight of 940 and ahydroxyl group value of 120 mgKOH/g and 65 g of a butyl acetate solutioncontaining 75 wt % of a trimer of hexamethylene diisocyanate blocked byβ-diketone were prepared and mixed with 710 g of propylene glycolmonomethyl ether and stirred until a uniform solution was obtained, 160g of a composite oxide sol 1 which consisted of TiO₂, Fe₂O₃ and SiO₂(TiO₂/Fe₂O₃/SiO₂=81/1/18 (weight ratio), titanium oxide was of ananatase type, dispersed in methanol, and had an average particlediameter of 10 nm and a nonvolatile content of 30%) was added, stirredand mixed until a uniform solution was obtained, and then 0.5 g of theFlorad FC-430 of 3M Co., Ltd. was added as a leveling agent and stirred.The obtained composition was designated as primer coat solution 1.

[0189] 1 g of Co(II) acetylacetonato dihydrate was added to 1,000 g ofthe separately prepared primer coat solution 1 and stirred to prepare aprimer coat solution 2.

[0190] 31 g of a polyester polyol comprising isophthalic acid and adipicacid (molar ratio of 6:4), 1,6-hexanediol and trimethylolpropane andhaving an average molecular weight of 650 and a hydroxyl group value of260 mgKOH/g, 68 g of a butyl acetate solution containing 75 wt % of atrimer of hexamethylene diisocyanate blocked by β-diketone and 634 g ofpropylene glycol monomethyl ether were stirred and mixed together untila uniform solution was obtained, 266 g of a composite oxide sol 2consisting of TiO₂, ZrO₂ and SiO₂ (TiO₂/ZrO₂/SiO₂=65/5/30 (weightratio), titanium oxide was of an anatase type, dispersed in methanol andhad an average particle diameter of 10 nm and a nonvolatile content of30%) was added, stirred and mixed until a uniform solution was obtained,and 0.5 g of the Florad FC-430 of 3M Co., Ltd. was added as a levelingagent and stirred. The obtained composition was designated as primercoat solution 3.

[0191] 61 g of a polyester polyol consisting of isophthalic acid and3-methyl-1,5-pentanediol and having an average molecular weight of 490and a hydroxyl group value of 226 mgKOH/g, 118 g of a propylene glycolmethyl acetate solution containing 70 wt % of a trimer of hexamethylnediisocyanate blocked by β-diketone and 630 g of propylene glycolmonomethyl ether were stirred and mixed together until a uniformsolution was obtained, 187 g of a composite oxide sol 3 consisting ofTiO₂, ZrO₂ and SiO₂(TiO₂/ZrO₂/SiO₂=79/1/20 (weight ratio), titaniumoxide was of a rutile type, dispersed in methanol and had an averageparticle diameter of 10 nm and a nonvolatile content of 30%) was added,stirred and mixed until a uniform solution was obtained, and 0.5 g ofthe Florad FC-430 of 3M Co., Ltd. was added as a leveling agent andstirred. The obtained composition was designated-as primer coat solution4.

[0192] 61 g of a polyester polyol consisting of adipic acid and3-methyl-1,5-pentanediol and having an average molecular weight of 485and a hydroxyl group value of 231 mgKOH/g, 119 g of a propylene glycolmethyl acetate solution containing 70 wt % of a trimer of hexamethylnediisocyanate blocked by β-diketone and 624 g of propylene glycolmonomethyl ether were stirred and mixed together until a uniformsolution was obtained, 187 g of the above composite oxide sol 3 wasadded, stirred and mixed until a uniform solution was obtained, 2 g of aCo(II) salt of 2-ethyl-hexylic acid was added and stirred, and 0.5 g ofthe Florad FC-430 of 3M Co., Ltd. was added as a leveling agent andstirred. The obtained composition was designated as primer coat solution5.

[0193] Preparation of Hard Coat Solutions 1 to 9.

[0194] 235 g of the same composite oxide sol 1 as used in thepreparation of the above primer coat solution 1 was weighed. 140 g ofdistilled water was added under agitation. 191 g ofγ-glycidoxypropyltrimethoxysilane and 42 g of tetramethoxysilane weregradually added. After the end of addition, they were stirred foranother 2 hours. Thereafter, 373 g of propylene glycol monomethyl etherwas added while the mixed solution was stirred and then 2 g oftetraethylene glycol monomethacrylate was added. 8 g of acetylacetonealuminum as a curing catalyst and 0.4 g of a silicone surfactant (L-7001of Nippon Unicar Co., Ltd.) as a leveling agent were further added andstirred for 1 hour. The above mixed solution was aged at roomtemperature for 48 hours to obtain a hard coat solution 1.

[0195] 235 g of the above composite oxide sol 1 was weighed. 140 g ofdistilled water was added under agitation. 191 g ofγ-glycidoxypropyltrimethoxysilane and 42 g of tetramethoxysilane weregradually added. After the end of addition, they were stirred foranother 2 hours. Thereafter, 373 g of propylene glycol monomethyl etherwas added while the mixed solution was stirred and then 2 g oftetraethylene glycol monomethacrylate was added. 8 g of acetylacetonealuminum as a curing catalyst and 0.4 g of a silicone surfactant (L-7001of Nippon Unicar Co., Ltd.) as a leveling agent were further added andstirred for 1 hour. 2 g of Co(II) acetylacetonato dehydrate was stillfurther added and stirred. The above mixed solution was aged at roomtemperature for 48 hours to obtain a hard coat solution 2.

[0196] 295 g of the above composite oxide sol 2 was weighed. 115 g ofdistilled water was added under agitation. 178 g ofγ-glycidoxypropyltrimethoxysilane was gradually added. After the end ofaddition, it was stirred for another 2 hours. Thereafter, 378 g ofisopropyl alcohol was added while the mixed solution was stirred andthen 15 g of tetraethylene glycol monomethacrylate was added. 7 g ofacetylacetone aluminum as a curing catalyst and 0.4 g of a siliconesurfactant (L-7001 of Nippon Unicar Co., Ltd.) as a leveling agent werefurther added and stirred for 1 hour. The above mixed solution was agedat room temperature for 48 hours to obtain a hard coat solution 3.

[0197] 295 g of the above composite oxide sol 2 was weighed. 115 g ofdistilled water was added under agitation. 178 g ofγ-glycidoxypropyltrimethoxysilane was gradually added. After the end ofaddition, it was stirred for another 2 hours. Thereafter, 378 g ofisopropyl alcohol was added while the mixed solution was stirred andthen 15 g of tetraethylene glycol monomethacrylate was added. 7 g ofacetylacetone aluminum as a curing catalyst and 0.4 g of a siliconesurfactant (L-7001 of Nippon Unicar Co., Ltd.) as a leveling agent werefurther added and stirred for 1 hour. 4.6 g of Co(II) acetylacetonatodehydrate and 2.3 g of 4,4′-thiobis(3-methyl-6-t-butylphenol) were stillfurther added and stirred. The above mixed solution was aged at roomtemperature for 48 hours to obtain a hard coat solution 4.

[0198] A hard coat solution 5 was obtained in the same manner as thehard coat solution 4 except that 6.9 g of a Co(II) salt of2-ethyl-hexylic acid was added in place of the Co(II) acetylacetonatodihydrate and 4,4′-thiobis(3-methyl-6-t-butylphenol) in the preparationof the hard coat solution 4.

[0199] 261 g of the above composite oxide sol 3 was weighed. 140 g ofdistilled water was added under agitation. 181 g ofγ-glycidoxypropyltrimethoxysilane was gradually added. Thereafter, 39 gof tetraethyl orthosilicate was added under agitation and then furtherstirred for 2 hours. Thereafter, 361 g of propylene glycol monomethylether was added while the mixed solution was stirred, and then 2 g oftetraethylene glycol monomethacrylate was added. 9 g of acetylacetonealuminum as a curing catalyst and 0.4 g of a silicone surfactant (L-7001of Nippon Unicar Co., Ltd.) as a leveling agent were further added andstirred for 1 hour. The above mixed solution was aged at roomtemperature for 48 hours to obtain a hard coat solution 6.

[0200] After 1 kg of the above hard coat solution 6 was preparedseparately, 2 g of Co(II) acetylacetonato dihydrate was added andstirred for 1 hour. The above mixed solution was aged at roomtemperature for 48 hours to obtain a hard coat solution 7.

[0201] 348 g of the above composite oxide sol 3 was weighed. 110 g ofdistilled water was added under agitation. 148 g ofγ-glycidoxypropyltrimethoxysilane was gradually added and furtherstirred for 2 hours. Thereafter, 368 g of propylene glycol monomethylether was added while the mixed solution was stirred, and then 11 g oftetraethylene glycol monomethacrylate was added. 6 g of acetylacetonealuminum as a curing catalyst and 0.4 g of a silicone surfactant (L-7001of Nippon Unicar Co., Ltd.) as a leveling agent were further added andstirred for 1 hour. The above mixed solution was aged at roomtemperature for 48 hours to obtain a hard coat solution 8.

[0202] After 1 kg of the above hard coat solution 8 was preparedseparately, 5.0 g of a Co(II) salt of 2-ethyl-hexylic acid was added andstirred for 1 hour. The above mixed solution was aged at roomtemperature for 4.8 hours to obtain a hard coat solution 9.

Examples 1 to 14 and Comparative Examples 1 to 8

[0203] The above primer coat solutions 1 to 5 were each applied to thefollowing two different lens substrates by the following methods andcured by heating and then the above hard coat solutions 1 to 9 were eachapplied to the above substrates by the following dip coating and curedby heating. The evaluation results of the properties of the obtainedcoated lenses are shown in Table 2. The thickness and refractive index(nD) of each film measured by the following methods are shown inTable 1. The results of a weatherability test measured by the followingmethod are shown in Tables 3 and 4.

[0204] Lens Substrate:

[0205] The following lens substrates A and B were used.

[0206] substrate A: plastic spectacle lens made from a thiourethaneresin having a refractive index of 1.594 and manufactured by molding andthermosetting the MR-6 monomer of Mitsui Toatsu Chemicals, Inc.

[0207] substrate B: plastic spectacle lens made from a thiourethaneresin having a refractive index of 1.66 and manufactured by molding andthermosetting the MR-7 monomer of Mitsui Toatsu Chemicals, Inc.

[0208] Application and Curing Methods of Primer Coat Solution:

[0209] The lens substrate is immersed in a primer coat solution, pulledup at a rate of 10 cm/min, dried at room temperature for about 10minutes and heated at 95° C. for 30 minutes to cure a coating film.

[0210] Application and Curing Methods of Hard Coat Solution:

[0211] The lens substrate (or substrate with a cured primer layer) isimmersed in a hard coat solution, pulled up at a rate of 15 cm/min,dried at room temperature for about 5 minutes and heated at 120° C. for1 hour to cure a hard coat layer.

[0212] Measurement of Film Thickness:

[0213] Each of the coat solutions is applied to a glass plate and iscured, part of the coating film is chipped off and the resulting leveldifference is measured to obtain the thickness of the film. It has beenconfirmed that whether the substrate is the above substrate A or B, thethickness of the obtained film remains the same as that of the aboveglass plate.

[0214] Measurement of Weatherability:

[0215] The appearance, adhesion and hardness of a film after 60, 120,180 and 240 hours of irradiation are evaluated as follows using a xenonweather-ometer weatherability tester (black panel temperature of 63° C.,water sprayed for 18 minutes every 2 hours, irradiation intensity of0.35 W/m² at 340 nm).

[0216] appearance: observed with the eye and ranked as follows.

[0217] A-no change

[0218] B-part of the lens slightly cracks

[0219] C-about ⅓ of the area of the lens cracks

[0220] D-all the surface of the lens cracks

[0221] adhesion: A cross-hatch test is conducted in accordance with across cut adhesion test JIS K5400. That is, 11 parallel lines are cut onthe surface of the film in both longitudinal and transverse directionsat intervals of 1 mm by a knife to form 100 squares and Cellotape isaffixed to the squares and then peeled off to count the number ofsquares adhered to the substrate from which the film is not peeled. Theproportion (%) of the number of the squares to the total number ofsquares is taken as adhesion.

[0222] hardness: The film is rubbed with steel wool #0000 10 times undera load of 1 kg to measure the scratching of the film based on thefollowing criteria.

[0223] 5: not scratched at all

[0224] 4: slightly scratched

[0225] 3: scratched

[0226] 2: badly-scratched

[0227] 1: scratched to the substrate TABLE 1 type of solution filmthickness (μm) refractive index primer 1 1.1 1.59 primer 2 1.2 1.59primer 3 1.1 1.66 primer 4 1.2 1.59 primer 5 1.2 1.59 hard coat 1 2.21.59 hard coat 2 2.2 1.59 hard coat 3 1.5 1.63 hard coat 4 1.5 1.63 hardcoat 5 1.5 1.63 hard coat 6 2.1 1.59 hard coat 7 2.1 1.59 hard coat 82.1 1.63 hard coat 9 2.1 1.63

[0228] TABLE 2 lens Primer hard coat No. substrate solution solutionadhesion hardness Ex. 1 A 1 2 100% 5 Ex. 2 A 2 1 100% 5 Ex. 3 A 2 2 100%5 Ex. 4 A none 2 100% 5 Ex. 5 B 3 4 100% 4 Ex. 6 B 3 5 100% 4 Ex. 7 Bnone 4 100% 4 Ex. 8 B none 5 100% 4 Ex. 9 A 5 7 100% 5 Ex. 10 A 6 6 100%5 Ex. 11 A 6 7 100% 5 Ex. 12 A none 7 100% 5 Ex. 13 B 3 9 100% 4 Ex. 14B none 9 100% 4 C. Ex. 1 A 1 1 100% 5 C. Ex. 2 A none 1 100% 5 C. Ex. 3B 3 3 100% 4 C. Ex. 4 B none 3 100% 4 C. Ex. 5 A 5 7 100% 5 C. Ex. 6 Anone 7 100% 5 C. Ex. 7 B 3 9 100% 4 C. Ex. 8 B none 9 100% 4

[0229] TABLE 3 weatherability test after 60 hours after 120 hours adhe-hard- adhe- appearance sion ness appearance sion hardness Ex. 1 A 100 5A 100 5 Ex. 2 A 100 5 A 100 5 Ex. 3 A 100 5 A 100 5 Ex. 4 A 100 5 A 1005 Ex. 5 A 100 4 A 100 4 Ex. 6 A 100 4 A 100 4 Ex. 7 A 100 4 A 100 4 Ex.8 A 100 4 B 100 4 C. Ex. 1 A 100 5 A 100 5 C. Ex. 2 A 100 5 A 100 5 C.Ex. 3 A 100 4 B 100 4 C. Ex. 4 A 100 4 B 100 4 weatherability test after180 hours after 240 hours adhe- hard- adhe- appearance sion nessappearance sion hardness Ex. 1 A 100 4 B 100 2 Ex. 2 B 100 3 C 100 2 Ex.3 A 100 4 B 100 2 Ex. 4 A 100 4 B 100 2 Ex. 5 A 100 3-4 B 100 2 Ex. 6 A100 3-4 B 100 2 Ex. 7 A 100 3-4 B 100 2 Ex. 8 A 100 3 B 100 2 C. Ex. 1 B0 2 D 0 1 C. Ex. 2 B 0 2 C 0 1 C. Ex. 3 C 0 2 D 0 1 C. Ex. 4 C 0 2 D 0 1

[0230] TABLE 4 weatherability test after 60 hours after 120 hours adhe-hard- adhe- appearance sion ness appearance sion hardness Ex. 9 A 100 5A 100 5 Ex. 10 A 100 5 A 100 5 Ex. 11 A 100 5 A 100 5 Ex. 12 A 100 5 A100 5 Ex. 13 A 100 4 A 100 4 Ex. 14 A 100 4 A 100 4 C. Ex. 5 A 100 5 A100 5 C. Ex. 6 A 100 5 A 100 5 C. Ex. 7 A 100 4 A 100 4 C. Ex. 8 A 100 4A 100 4 weatherability test after 180 hours after 240 hours adhe- hard-adhe- appearance sion ness appearance sion hardness Ex. 9 A 100 5 A 1004 Ex. 10 A 100 4 B 100 3-4 Ex. 11 A 100 5 A 100 4 Ex. 12 A 100 5 A 100 4Ex. 13 A 100 4 A 100 3-4 Ex. 14 A 100 4 A 100 3-4 C. Ex. 5 A 100 2-3 B 01-2 C. Ex. 6 A 100 2 A 0 1-2 C. Ex. 7 B 100 2 B 0 1-2 C. Ex. 8 B 100 2 B0 1-2

[0231] Examples 1 to 14 and Comparative Examples 1 to 8 are satisfactoryin terms of appearance, film adhesion and film hardness after 120 hoursof a weatherability test but differences in these properties is observedamong them after 180 hours of the weatherability test.

[0232] Film adhesion is satisfactory even after 240 hours in Examples 1to 14 but film adhesion is lost after 240 hours in Comparative Examples1 to 8.

[0233] When anatase type titanium oxide is used, film hardness issatisfactory after 180 hours in Examples 1 to 8 but it deterioratesafter 180 hours in Comparative Examples 1 to 4. When rutile typetitanium oxide is used, film hardness is satisfactory after 240 hours inExamples 9 to 14 but it deteriorates after 180 hours in ComparativeExamples 5 to 8. When anatase type titanium oxide is used, Examples 1 to8 are superior in film appearance to Comparative Examples 1 to 4. Whenrutile type titanium oxide is used, both Examples and ComparativeExamples are satisfactory after 240 hours.

[0234] According to the present invention, there can be obtained aplastic spectacle lens which prevent the cracking and peeling off of ahard coat layer or primer layer and a reduction in film hardness and hasexcellent durability, and other coated articles.

1. A plastic lens comprising a plastic lens substrate having arefractive index of 1.50 or more, a primer layer which is formed on thesurface of the substrate, and a hard coat layer which is formed on thesurface of the primer layer and comprises a silicon resin as a resincomponent, the primer layer comprising: (1) 2 to 70 wt % of titaniumoxide or a composite oxide thereof having a particle diameter of 1.0 to100 nm, the titanium oxide containing at least one titanium oxideselected from the group consisting of rutile type titanium oxide andanatase type titanium oxide in an amount of 50 wt % or more; (2) 1 to 10wt % of a chelate compound or fatty acid salt containing Co(II); and (3)20 to 97.9 wt % of an urethane resin, and having a refractive index of1.48 or more and a thickness of 0.5 to 5 μm, the weight percentages ofthe above components (1), (2) and (3) being based on 100 wt % of thetotal weight of the components (1), (2) and (3).
 2. The plastic lens ofclaim 1 which further has an anti-reflection layer on the exteriorsurface of the hard coat layer.
 3. The plastic lens of claim 1, whereinthe primer layer has been formed from a solution composition comprising:(1) 2 to 70 wt % of titanium oxide or a composite oxide thereof having aparticle diameter of 1.0 to 100 nm, the titanium oxide containing atleast one titanium oxide selected from the group consisting of rutiletype titanium oxide and anatase type titanium oxide in an amount of 50wt % or more; (2) 1 to 10 wt % of a chelate compound or fatty acid saltcontaining Co(II); (3) 10 to 87.9 wt % of a polyol; and (4) 10 to 87.9wt % of a polyisocyante, the weight percentages of the above components(1), (2), (3) and (4) being based on 100% of the total weight of all theabove components